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Патент USA US3033838

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United States Patent 0 ” lC€
3,033,828
.
Patented May 8, 1962
2
1
least 8 carbon atoms which is not part of the main hydro
3,033,828
OIL-SOLUBLE OXYGEN-CONTAINING POLYMERS
carbon polymer chain includes polymerizable esters, and/
or amides of unsaturated acids.
Suitable esters include
Richard C. Nelson, 2260 Hillside Court,
Walnut Creek, Calif.
No Drawing. Filed Feb. 23, 1960, Ser. No. 10,061
acrylic and alkacrylic esters of aliphatic alcohols of at
least 8 carbon atoms, preferably of from 10 to 20 car
6 Claims- (Cl. 260-775)
acrylate, stearyl acrylate, eicosanyl acrylate, docosanyl
acrylate, decyl methacrylate, lauryl methacrylate, cetyl
This invention relates to new polymeric products. More
bon atoms, and include, inter alia, decyl acrylate, lauryl
methacrylate, stearyl methacrylate, and the like, and mix
containing polymeric compounds having a long linear 10 tures thereof.
Other substances include the vinyl esters of long-chain
hydrocarbon backbone chain which is particularly useful
carboxylic acids such as vinyl laurate, vinyl palmitate,
as detergents, wear inhibitors and stabilizers for liquid
particularly, it relates to a new class of oil-soluble polar
hydrocarbon compositions.
It is an object of the invention to provide a new class
vlnyl stearate, vinyl oleate and the like and mixtures there
of; long-chain esters of vinylene dicarboxylic acids such
of polymeric compounds. It is a further object to pro 15 as methyl lauryl fumarate; and methyl stearyl maleate,
N-long chain hydrocarbon substituted amides of unsat
vide a new oil-soluble polymeric compound having a
urated acids such as N-stearyl methacrylamide, N-lauryl
long hydrocarbon backbone chain and a polar radical at
methacrylamide, N-stearyl acrylamide and the like.
tached thereto through a methylene group. It is a
These components can be employed alone or in various
further object to provide new polymers which are useful
as detergents, and wear inhibitors for petroleum products 20 combinations. The technical lauryl methacrylate ob
tained from the commercial mixture of long-chain alco
such as lubricating oil and fuel compositions. These and
hols in the C10 to C18 range derived from coconut oil
other objects of the invention will be apparent from the
is an especially useful oleophilic component of the co
following detailed description thereof.
polymer. The group of acrylic and alkacrylic esters of
It has now been discovered that these and other ob
jects may be accomplished by the new and novel poly 25 aliphatic alcohols of at least eight carbon atoms are, in
general, well suited as the oleophilic component of the
meric products of the invention which comprise oil-soluble
polymeric compounds having essentially a long linear hy
copolymer.
The copolymers of allyl or methallyl alcoholsv and
esters of methacrylic acid and C1048 fatty acids, e.g.,
being an oil-solubilizing oleophilic hydrocarbon radical, 30 lauryl and/or stearyl methacrylate are preferred. Co
polymers of this type can be prepared by polymerizing
preferably an alkyl radical having an average of between
an ester of acrylic or methacrylic acid such as lauryl or
8 and 20 carbon atoms, preferably 10-18, bonded indi
stearyl methacrylate with an excess of allyl alcohol or by
rectly thereto through an oxygen-containing polar group
hydrolyzing copolymers of allyl esters, such as allyl ace
such as an ester or an amide group, and the other being
a polar-containing group —CH2-X, wherein Xyis a 35 tate or propionate, and an ester of methacrylic acid such
as lauryl methacrylate. The method of preparing co
polar group such as hydroxy, carboxyl, cyano, sulfo,
polymers by the latter process is to hydrolyze copolymers
amine, amide or carbamyl, preferably a hydroxyl, an
obtained by reacting an oleophilic-containing monomer,
amine, an amide or a carbamyl group.
such as a long chain alkyl ester of an acrylic acid, e.g.,
Oil-soluble polymers of this type are prepared by re
acting an allyl compound, e.g., allyl alcohol, allyl ester, 40 lauryl or stearyl methacrylate with a large excess of an
allyl ester such as allyl acetate or allyl propionate. At
allyl amine or an allyl amide and a polymerizable ester
least 70%, preferably over 90%, of the allyl ester groups
or amide ‘having an oleophilic radical such as a long
should be converted to free hydroxyl groups.
alkyl radical of at least 8, preferably from 10 to 18 car
The following examples are given as representative
bon atoms, such as C1040 alkyl esters of acrylic or meth
drocarbon backbone chain and attached thereto, in a
uniform or random fashion, two essential groups, one
acrylic acids, vinyl esters of long-chain fatty acids having 45 embodiments of the invention.
Example I
mixtures thereof. copolymers of allyl compounds and
at least 8 carbon atoms, N—-C1o_gn alkyl acrylamides, and
long-chain alkyl esters of acrylic acids, such as esters of
To 29.5 moles of allyl alcohol at 80-100" C. were
e.g., from 1:1 to 15:1, preferably from 5:1 to 10:1, re
reacted monomers were removed by distillation, and the
oil-soluble copolymer had a molecular weight of about
added each hour for seven hours 2.744 moles of lauryl
methacrylic acid and Ca_C,o fatty acids, are preferred.
The mol ratio of the allyl compound to the oleophilic 50 methacrylate and 0.00793 mole of alpha,alpha’-azodi-iso
butyronitrile. After eight hours polymerization, the un
ester or amide can vary within relatively wide limits,
spectively, and the polymer may have suitable molecular
10,000.
weights of from about 1,500 to over one million, pref
65
Example I!
erably between 10,000 and 100,000.
The copolymerization may be carried out in the pres
10 moles of allyl acetate and 1 mole of lauryl meth
ence of a suitable oxygen-yielding initiator, such as a
acrylate were reacted in the presence of ditertiary butyl
suitable peroxide or azo compound and at temperatures
peroxide at 80-100° C. for 2 to 8 hours.
varying from room temperature to about 150° C.
The copolymer was then mixed with a mixture of
60
-The allyl compounds used to form the copolymers,
inter alia, include allyl alcohol, methallyl alcohol, allyl
acetate, allyl propionate, allyl butyrate methallyl acetate,
allyl amine, N,N-diethyl allylamine, N-allyl aniline, allyl
methanol and ethanol and sodium methacrylate so as to
effect a 95% conversion of the acetate group to hydroxyl
groups. The sodium acetate formed was removed by
allyl carbamate, and mixtures thereof.
Polymerizable monomers containing oleophilic com
ponents containing an aliphatic hydrocarbon chain of at
about 50,000.
washing with isopropanol-water mixture and the result
formamide, esters of allyl alcohol and a carbamic acid,
' e.g., allyl carbamate, methallyl carbamate, N,N-diethyl 65 ing oil-soluble copolymer had a molecular weight of
.
The following examples further illustrate polymeric
additives used in compositions of the present invention.
8,083,828
Example
Temp.,
Catalyst
° C.
Mole Ratio of Allyl Compound/Olso- - Degree oi
phllic Monomer
HydigolY3
III........ .- benzoyl perioxide.-.
1001 allyle a(llcohol (10)/stearyl methacry-
IV.............. --do ............. __
100
a
‘
Mol.
Wt.
.
25,000
.
allyl alcohol (l5)/mixtu.re of lauryl and .......... _.
30, 000
gteiaryl methacrylate (1) in ratio 01'
v.......... _- dltertbutyl peroxide.
115 allyl 311mm (10)]N-stearyl methacryl-
VI .............. _-do............. .V11’
dn
115 allyl alcohol (10)/1sury1methacrylate__
115 , allyl acetate (10)]1auryl acrylate ..... _-
VIII....... __ benmy1peroxide.--IX.
do
X-“
do
80
100
85
methallyl acetate (10)/stearyl aerylate.
.90
atlylamlne (10),’lauryl methacrylamide. .......... -allyl alcohol (12)]vinyl stearate .................. --
15, 000
10, 000
X1..-
100
aliylecarbamate (10)]lauryl '- ‘L ""y-
15' 000
am
do
a
m, 000
e.
90
20,000
,000
10,000
.
Polymeric products of this invention are outstanding
additives for various liquid hydrocarbon products, such
as natural and synthetic hydrocarbon lubricating oils,
greases, fuels (gasoline, gas oil, burner fuel oil), a'sphalts,
waxes, slushing oils, industrial oils, e.g., metal working
and drawing oil, quenching oils, textile oils, dielectric
ate and Ca, Ba or Zn salt of octyl phenol-formaldehyde
20 condensation product, etc., can be used in conjunction
with the polymers of this invention.
To illustrate the manner in which the invention may be
carried out, the following examples are given. It is to
be understood, however, that the examples are for the
compositions and other industrial oils. They are par 25 purpose of illustration and the invention is not to be re
ticularly outstanding when added in small amounts to
garded as limited to any of the speci?c materials recited
lubricating oils and lubricating compositions to impart
therein.
detergency and anti-wear properties to such materials.
The improvement imparted to oils by polymers of this
Also, they are useful additives for gasoline, fuel oils and
invention is shown by the following test results. To a
other light oil products.
30 mineral oil (150 SUS 210° F.) having an L1 engine
The novel polymers are effective in liquid hydrocarbon
rating for top ring groove ?lling of 100 (100=poor,
compositions such as mineral lubricating oil compositions
0=perfect) and an EX-3 engine cleanliness rating of 53
in ranges from about 0.001% to about 10%, preferably
(100=perfect, 50=poor) was added 10% basic calcium
from about 0.02% to about 1% by weight. The lubricat
petroleum sulfona-te and 0.75% zinc dihexyl dithiophos
ing stock for this purpose can be any natural or synthetic 35 phate (composition X) and the EX-3 rating was in
hydrocarbonaceous material having lubricating properties.
creased to 65. However, when 1% of additive of Exam
Thus, the base may be a hydrocarbon oil of wide viscosity
ple I was added to composition X (composition A) the
range, e.g., 100 SUS at 100° F. to 150 SUS at 210° F.
EX-3 rating was increased to 70. A mineral oil ('150
The hydrocarbon oils may be blended with ?xed oils such
SUS 210° F.) containing 10% basic calcium petroleum
as castor oil, lard oil and the like, and/or with synthetic 40 sulfonate, 1.2% zinc dihexyldithiophosphate and 5% co
lubricants such as polymerized ole?ns, copolymers of
polymer of lauryl methacrylate/2-methyl-5-vinyl pyridine
alkylene glycols and oxides; organic esters of polybasic
(composition Y) gave an L-1 rating of 85; however, when
organic and inorganic acids, e.g., di-Z-ethylhexyl sebacate,
the vinyl pyridine copolymer in composition Y was re
dioctyl phthalate, trioctyl phosphate; polymeric tetrahy
placed with 1% of additive of Example I (composition
drofuran; polyalkyl silicone polymers, e.g., dimethyl sili 45 B) the L-l rating was reduced to 10. The L-l engine
cone polymer and the like. In addition the base can be
test is described in the CRC Handbook and the EX-3
gasoline, fuel oils or greases.
engine test (6 cylinder) is essentially the same as described
In addition to the above-described lubricating oil com
in SAE preprint 18, Detroit, Meeting Jan. 15-17, 1958.
positions such composition can be modi?ed with small
When various amounts of from 0.1% to 10% of the
amounts of other additives (0.01-2%) such as pour point 50 polymeric material of Examples II to X are incorporated
depressants, viscosity index improyers, blooming agents,
in various mineral oils such as SAE 10, 20, 30, low-30
corrosion inhibitors, oiliness agents, solubilizer, and the
and similarly tested as noted above, bene?cial results are
like. Among such materials are-high-molecular-weight
obtained as a result of the polymeric additives of this
polymer, e.g., “Acyloids,” which are polymeric esters of
invention.
.
methacrylic acid and long-chain fatty alcohols, e.g., mix 55 This application is a continuation-in-part of copending
tures of wax-naphthalene condensation products, isobutyl
application Serial No. 742,505, ?led June 17, 1958.
ene polymers, alkyl styrene polymers; inorganic and or
I claim as my invention:
ganic nitrites such as NaNO, and diisopropylammonium
1. An oil-soluble copolymer of (1) an allylic com
nitrite and dicyclohexylammonium nitrite; organic phos
pound selected from the group consisting of an allyl
phites, phosphates and phospbonates such as trichloro 00 alcohol, an allyl amine, and an allyl carbamate and (2)
ethyl phosphite, tricresyl phosphate, dilorolphosphate,
a polymcrizable ester selected from the group consisting
phosphorus sul?de-ole?nic reaction products such as
of a C1048 alkyl acrylate and a vinyl carboxylate having
Pasg-terpene reaction products, metal organic phosphates,
from 10 to 18 carbon atoms in the molecule, in the mol
e.g., Ca or Zn dicyclohexylthiophosphate or Z-ethylhexyl
ratio of ( 1) to (2) of from 1:1 to 15:1 respectively, the
thiophosphate; organic sul?des, e.g., wax disul?de, ethyl 65 copolymer having a molecular weight of at least 1500.
ene bistolyl sul?de; amines, e.g., octadecylamine and the
2. An oil-soluble copolymer of allyl alcohol and a
like. Also, phenolic antioxidants such as 2,6~diter,tiary
Cm_1a-alkyl acrylate in the mol ratio of 1:1 to 15:1,
4-methyl phenol, 2,6 - ditertiary-4-methylol phenol, and
respectively, and having a molecular weight of at least
2,2'-methylene bis(4-methyl-o-tertiarybutylphenol) as well 70 1500.
as conventional metallic detergents of the sulfonate and
3. An oil-soluble copolymer of allyl alcohol and lauryl
phenate class exempli?ed by alkali and alkaline earth
methacrylate in the mol ratio of 1:1 to 15:1, respectively,
organic sulfonates and phenates, e.g., Na, basic Ca or
and having a molecular weight of at least 1500.
basic Ba petroleum sulfonate and Na, Ca, Ba, or Zn
4. An oil-soluble copolymer of allyl alcohol and lauryl
cetyl phenate, basic Ca or basic Ba C3-C1, alkyl salicyl
methacrylate in the mol ratio of 5:1 to 10:1, respectively,
3,033,323
and having a molecular weight between 10,000 and
100,000.
5. An oil~so1uble copolymer of allyl carbamate and a
Cm__m-alkyl methacrylate, in the mol ratio of 1:1 to 15: 1,
respectively, and having a molecular weight of at least
1500.
6. An oil-soluble copolymer of allyl carbamate and
Iauryl methacrylate, in the mol ratio of 15:1 to 1:1, re
spectively, and having a molecular weight of at least
10
1500.
6
References Cited in the ?le of this patent
UNITED STATES PATENTS
2,600,383
2,600,421
2,600,446
2,600,448
2,892,786
2,892,791
2,892,793
2,892,818
Bauer et a1. ......... __ June 17, 1952
Neher et al ___________ _- June 17, 1952
Van Horne et a1. ..... __ June 17, 1952
Van Horne et al. ..... -_ June 17, 1952
Stewart et a]. ________ .._
Lowe et al. __________ .....
Stewart et al. ________ .__
Lowe et al. __________ -__
June
June
June
June
30,
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1959
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1959
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